US4980196A - Method of coating steel substrate using low temperature plasma processes and priming - Google Patents

Method of coating steel substrate using low temperature plasma processes and priming Download PDF

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Publication number
US4980196A
US4980196A US07/480,356 US48035690A US4980196A US 4980196 A US4980196 A US 4980196A US 48035690 A US48035690 A US 48035690A US 4980196 A US4980196 A US 4980196A
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United States
Prior art keywords
plasma
steel substrate
organosilane
gas
thin film
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US07/480,356
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English (en)
Inventor
Hirotsugu Yasuda
Tyau-Jeen Lin
Duck J. Yang
Joseph A. Antonelli
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority to US07/480,356 priority Critical patent/US4980196A/en
Assigned to E.I. DU PONT DE NEMOURS AND COMPANY, WILMINGTON, DE A CORP. OF DE reassignment E.I. DU PONT DE NEMOURS AND COMPANY, WILMINGTON, DE A CORP. OF DE ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: LIN, TYAU-JEEN, YASUDA, HIROTSUGU, ANTONELLI, JOSEPH A., YANG, DUCK J.
Priority to BR909007994A priority patent/BR9007994A/pt
Priority to KR1019920701946A priority patent/KR0143884B1/ko
Priority to ES90916927T priority patent/ES2098275T3/es
Priority to EP90916927A priority patent/EP0515373B1/en
Priority to JP2515713A priority patent/JP2843670B2/ja
Priority to PCT/US1990/006405 priority patent/WO1991012092A1/en
Priority to AU67216/90A priority patent/AU652544B2/en
Priority to DE69030107T priority patent/DE69030107T2/de
Publication of US4980196A publication Critical patent/US4980196A/en
Application granted granted Critical
Priority to CA002035991A priority patent/CA2035991C/en
Priority to NZ237089A priority patent/NZ237089A/en
Priority to MX024521A priority patent/MX173224B/es
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/62—Plasma-deposition of organic layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • B05D3/141—Plasma treatment
    • B05D3/142—Pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • B05D3/141—Plasma treatment
    • B05D3/145—After-treatment
    • B05D3/147—Curing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
    • C23C16/0245—Pretreatment of the material to be coated by cleaning or etching by etching with a plasma
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/503—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using dc or ac discharges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/10—Metallic substrate based on Fe
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2451/00—Type of carrier, type of coating (Multilayers)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2518/00—Other type of polymers
    • B05D2518/10—Silicon-containing polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • B05D7/542—No clear coat specified the two layers being cured or baked together

Definitions

  • This invention relates to the use of low temperature plasma technology for the corrosion protection of steel.
  • Our novel process involves reactive or inert gas plasma treatment of the steel, followed by plasma thin film deposition of an organosilane on the treated substrate (which is conducted at ambient temperatures and does not require baking), and finally application of an appropriate primer.
  • Our deposition step process is conducted at ambient temperatures, utilizes DC power with the steel substrate as the cathode, and the anodes are equipped with magnetic enhancement (magnetron).
  • the corrosion protection of steel substrates is an important industrial process. This process is important for many industries including the automotive industry, steel industry and so forth. Currently the most common methods of corrosion protection of steel substrates are galvanizing, zinc phosphate, electrodeposition of organics, conventional spray or dip priming, oil coating and so forth. However, in the automotive industry and other high performance uses these methods have the following problems: (1) pollution in the form of Volatile Organic Content (VOC), (2) excessive waste disposal, (3) inadequate coverage of recessed areas, and (5) inadequate long corrosion protection performance.
  • VOC Volatile Organic Content
  • the process utilizes AC power, system pressures of 1-5 torr and does not disclose pretreating the steel by reactive (e.g. oxygen) or inert gas (e.g.argon) plasma or a mixture thereof
  • reactive e.g. oxygen
  • inert gas e.g.argon
  • the "Glow Discharge" process would not be a viable method for long term corrosion protection of steel such as is necessary in the automotive industry.
  • What is needed is a method of depositing a thin film layer on a variety of different steel substrates to give improved corrosion resistance.
  • the method must result in a film having good adhesion, good edge coverage, good barrier properties and the method must have minimal VOC problems and minimal waste disposal.
  • This postprocessing step can be done to enhance the adhesion between the plasma film and the primer coating.
  • This post processing of the plasma layer preferably results in polarization of the surface of the plasma film layer by forming hydroxyl, acid or base groups which may then react with the primer coating.
  • the post processing step typically involves reactive plasma gas such as oxygen, water, ammonia, etc. or inert plasma gas such as helium, argon, etc.
  • FIG. 1 is a schematic of our plasma deposition system showing the vacuum chamber, electrodes, power source, related piping and so forth.
  • FIG. 2 is a frontal view of one of the anodes equipped with a magnetron.
  • FIG. 2A is a side view of the same anode in FIG. 2.
  • the novel system consists of four basic steps.
  • the first step is pretreatment of the steel substrate with inert or reactive plasma gas.
  • the second step is plasma deposition of a thin film.
  • the third (optional step) is plasma post treatment of the surface of the thin film
  • the fourth step is the coating of a primer over the post-treated plasma film.
  • the first step involving the plasma pretreatment with inert or reactive gas is preferable to conventional cleaning and results in better adhesion. (If the steel substrate is oiled, it should be cleaned by conventional methods such as solvent cleaning prior to this plasma processing).
  • the second step is coating the steel substrate with a thin layer or layers of plasma formed organic polymer in a highly evacuated chamber.
  • an optional third step is post treatment of the surface of the thin film to enhance the adhesion between the plasma film and the primer coating to be applied over it.
  • This post processing of the plasma layer preferably results in functional groups such as hydroxyl, acid or base which may then react (or be compatible) with the primer coating.
  • the post processing step typically involves reactive plasma gas such as oxygen, water, ammonia, etc. or inert plasma gas such as helium, argon, etc.
  • the fourth step, application of the primer can be done in a variety of ways. The important thing is to pick a primer which has good adhesion to the plasma deposited film, good barrier properties and good corrosion protection.
  • FIG. 1 shows vacuum chamber 11, cathode 12 (which is the steel substrate), anodes 13, power supply 14, plasma gas feeding line 15, plasma gas flow controllers 16 and vacuum pump 17.
  • the negative pole of DC power supply 14 is connected to the steel substrate to form cathode 12.
  • the grounded positive pole of DC power supply 14 is connected to anodes 13.
  • anodes 13 are equipped with a superimposed magnetic field (magnetron).
  • the magnetron is imperative for the plasma deposition step but is not necessary for the plasma pretreatment step or the plasma post-treatment step.
  • the magnetic field at the magnet surface should be between 10-10,000 Gauss, preferably 100-1000 Gauss and most preferably 700 to 900 Gauss.
  • Magnetrons are well known in the art and are generally disclosed in the Thin Film Processes book (cited above) at Part II-2 and Part II-4. As will be apparent to one skilled in the art there are numerous ways to superimpose the magnetic field.
  • FIG. 2 is a detail of the anode arrangement that we used in our examples (The exact dimensions are detailed in the Example Section).
  • Anode 13 is composed of aluminum plate 23; titanium plate 22 (which is attached on inner side of aluminum plate 23); iron ring 24 and circular iron plate 24' (which are attached on the backside of aluminum plate 23); and 8 permanent magnetic bars 25 (which are attaced on circular iron plate 24 and iron ring 24' with the south poles facing the center point).
  • the magnetic field strength ranges from 700-900 gauses.
  • the whole electrode (anode) 13 is then supported by ceramic materials 26.
  • the anode configuration can be varied as well as the materials of construction of the anode.
  • titanium plate 23 or aluminum plate 22 could be made of other paramagnetic materials with low sputtering yields
  • circular iron plate 24' or iron ring 24 could be made of other ferromagnetic materials.
  • the steel substrate is hung at the center between two parallel anodes 13 and the steel substrate is connected to the negative pole of DC power supply 14 so that the steel substrate becomes cathode 12.
  • Vacuum pump 17 is then used to evacuate vacuum chamber 11 until the system pressure is lower than 1 millitorr.
  • the system pressure is controlled, independent of the gas flow rate, by throttle valve 18, using the reading of pressure gauge 19.
  • the pretreatment gas or gases e.g.
  • oxygen gas or oxygen gas plus argon is fed into vacuum chamber 11, at the desired flow rate, keeping the pressure below 1 torr, preferably less than 100 millitorr.
  • Our preferred pretreatment gas is oxygen because it removes organic contaminants and may form metal oxides on the surface of the steel substrate.
  • Other reactive gases or inert gases or their mixtures can be used. These other pretreatment gases include air, hydrogen, nitrogen, argon, water vapor and so forth.
  • W electric power input
  • F the molar flow rate
  • M the molecular weight of gas.
  • FM represents the mass of low rate.
  • the pretreatment plasma gas is fed through plasma gas feeding line 15 and the rate is controlled by using the appropriate plasma gas flow controller 16. Then power supply 14 is turned on to initiate the plasma state. The power is then adjusted to the desired power level. This power level varies dependent on flow rate, size of substrate, distance from cathode to anode, molecular weight of the pretreatment gas, pressure and so forth.
  • the pretreatment plasma should be maintained for a desired period of time (typically from 30 seconds to 10 minutes) and then power supply 14 should be turned off and the pretreatment gas flow should be stopped using the appropriate plasma gas shut off valve 20.
  • the treatment time depends on the operating parameter W/FM Efficient treatment can be obtained by maintaining the "(energy input) multiplied by (treatment time) divided by (mass)" at between 0.5 GigaJoule-Second per Kilogram and 50 GigaJoule-Sec per Kilogram.
  • the vacuum chamber 11 should once again be evacuated using vacuum pump 17 to a pressure of below 1 millitorr. This concludes the plasma pretreatment step.
  • RF radio frequency
  • the power is turned on and then adjusted to the desired power level.
  • This power level varies dependent on flow rate, size of substrate, distance from cathode to anode, molecular weight of the plasma gas, pressure and so forth.
  • the plasma deposition should continue for a desired period of time in order to obtain the desired film properties and thickness.
  • the film thickness can range between 10 Angstroms to 10 micrometers, preferably 10 Angstroms to 5,000 Angstroms and most preferably 10 Angstroms-3000 Angstroms.
  • the deposition time is typically from 1 second to 20 minutes, preferably 30 seconds to 10 minutes and most preferably 30 seconds to 2 minutes.
  • Control of the deposition process may also be based upon the "(energy input) multiplied by (deposition time) divided by (mass)". This parameter should be kept between 0.5 GigaJoule-Second per Kilogram and 50 GigaJoule-Sec per Kilogram.
  • power supply 14 is turned off and the plasma gas flow should be stopped using the appropriate plasma gas shut off valve 20.
  • the deposition time depends on the power input level divided by mass expressed in Joule per Kilogram. Deposition that is efficient for corrosion resistance is dependent on film adhesion, film barrier properties and film thickness.
  • TMS trimethylsilane
  • Alternatives include but are not limited to dimethylsilane (DMS), tetramethylsilane, trimethylethoxysilane, methyltrimethoxysilane, hexamethyldisiloxane or other organosilanes which contain either silicon, oxygen, carbon, phosphorous, or hydrogen or their mixtures, and with or without vinyl unsaturation.
  • DMS dimethylsilane
  • tetramethylsilane trimethylethoxysilane
  • methyltrimethoxysilane hexamethyldisiloxane or other organosilanes which contain either silicon, oxygen, carbon, phosphorous, or hydrogen or their mixtures, and with or without vinyl unsaturation.
  • Other hydrocarbons containing carbon, hydrogen, oxygen, flouride or their mixtures e.g methane
  • the carrier gas can be inert gases such as argon and helium or reactive gases such as oxygen or nitrogen (or mixtures thereof).
  • Liquid or even solid compounds can also be used as the plasma deposition compound if enough vapor pressure can be created for the compounds to feed into the vacuum system. Gas materials at room termperature are preferred for the purpose of maintaining constant flow rate.
  • vacuum chamber 11 should be evacuated using vacuum pump 17 to a pressure of below 1 millitorr. This concludes the deposition step. It should be pointed out, however, that further layers of plasma film may be deposited on top of the first layer. These subsequently deposited layers would probably be organics or organometallics other than silanes. While it is imperative that the first layer be deposited as set out above (i.e. D.C. power, with a magnetron on the anode(s)), the subsequently deposited plasma layers could be deposited using alternate power methods known in the art (e.g. A.C. power, microwave, and Radio Frequency (RF) power).
  • RF Radio Frequency
  • the third step in our process is the optional post treatment step of the surface of the deposited plasma film.
  • This step could be important because post treatment of the surface of the deposited plasma film layer before it is covered by the primer coating may enhance the adhesion between the plasma film layer and the primer coating. However, in certain cases, for economic reasons (i.e. shorter processing time for higher productivity), it may be desirable to skip the post treatment step of the surface of the plasma film and proceed directly to the primer coating step.
  • This post treatment of the plasma film layer preferably makes the surface polar by generating hydroxy groups, acid groups, or base groups (e.g. amines, alkyl amines, amide and so forth).
  • the post treatment step typically involves another plasma treatment with nonpolymerizing reactive gases such as oxygen, water, carbon dioxide, or ammonia (or their mixtures) with or without inert gas(es).
  • An example of post treatment of the plasma film is shown in Example V.
  • a traditional primer coating cover is applied.
  • the steel substrate with the plasma deposited thin film has superior corrosion protection than the same steel without the thin film, but the corrosion protection is dramatically improved after the application of the primer coating Likewise, a steel substrate with both a thin film plasma deposited layer and primer coating has superior corrosion protection to a steel substrate with only the primer coating.
  • the primer can be applied in any of a number of different manners well known in the art (e.g. cathodic or anodic electrocoating, dipping, spraying, rolling, powder coatings, vacuum deposition polymerization and so forth). Furthermore any of a number of different primer coatings well known in the art may be used. Examples include but are not restricted to acrylic silane, polyester silane, polyester urethane-silane, melamine/polyester, melamine/polyester urethane, epoxy anhydride, epoxy amine, polyester isocyanate, polyether vinyls and so forth.
  • a preferred primer coating is one which is reactive with the plasma deposited film.
  • primers such as acrylic silane, polyester silane or polyester urethane-silane, (i.e. primers which contain silanol and alkoxy silane groups) are preferred.
  • a most preferred primer is a trimethoxysilane containing resin. This type of primer is generally described in Kanegafuchi patent No. U.S. 4,801,658.
  • the primer formula may or may not contain catalysts (or accelerators), such as dialkyl tin oxide compounds, H 2 O, acids, or organotitanates or organozirconates.
  • catalysts or accelerators
  • dialkyl tin oxide compounds such as dialkyl tin oxide compounds, H 2 O, acids, or organotitanates or organozirconates.
  • the primer thickness can vary widely. Primer films of 2.5 microns to 125 microns thick can be coated on steels, but a preferred thickness range is 10.0 microns to 50 microns.
  • primer subsequent top coats may also be applied. These include primer surfacers, monocoats, basecoat/clearcoat or any other topcoat system known in the art.
  • Vacuum chamber Pyrex® bell-jar of 18" in diameter and 30" in height
  • Cathode is the steel substrate described above positioned between two anodes;
  • Each anode is composed of aluminum plate 23 (7" ⁇ 7" ⁇ 1/2"), a titanium plate 21 (7" ⁇ 7" ⁇ 1/16") which is attached on inner side of aluminum plate 23, an iron ring 24 (7" in outer diameter, 5.5" in inner diameter, 1/16" thick) and iron plate 24 (2" in diameter, 1/16" thick) which are attached on the backside of aluminum plate 23, and 8 pieces of permanent magnetic bars 25 (3" ⁇ 1/2" ⁇ 1/4") which are attaced on the iron plate 24 and iron ring 24 with the south poles facing the center point.
  • the magnetic field strength ranges from 700-800 gauses.
  • the whole electrode (anode) 13 is then supported by ceramic materials 26:
  • the cathode is positioned between the two parallel anodes with the titanium side facing the cathode at a distance of 2".
  • Vacuum Pumping Mechanism A mechanical booster pump (available from Shimadzu Corporation as model MB-100F) in series with a mechanical rotary pump (availble from Sargent-Welch Scientific Company as model 1376).
  • Throttle valve available from MKS Instruments as model 253A
  • throttle valve controller also available from MKS Instrument as model 252A
  • test panels are scribed
  • the scribe line is at the center of the panel and is about 3 inches long. These scribed panels are then subjected to the following test cycle:
  • Samples remain in humidity cabinet (85% R.H., 60° C.) Samples were examined occasionally. After completion of the Scab corrosion test, the test panels were removed from the chamber and rinsed with warm water. The samples were examined visually for failure such as corrosion, lifting, peeling, adhesion loss, or blistering.
  • scribe line corrosion creepback loss of adhesion between primer and steel
  • the average of multiple measurements is calculated.
  • Substrate cleaned cold-rolled steel coupon. (Available from ACT Corp. Product designation GMC 92A.)
  • O 2 plasma pretreatment conditions DC power was 12 watts and 600-800 volts; energy input per mass was 0.25 gigaJoules per kilogram; oxygen gas flow rate was 2 standard cubic centimeter per minute (sccm); system pressure was 30 milliTorr; and power duration was 2 minutes.
  • primer coating The substrate was removed from the vacuum chamber and the primer was applied.
  • the primer which was applied was our most preferred primer containing methoxysilane functional group. This resin is described in Kanegafuchi Patent No. U.S. 4,801,658.
  • the primer was applied to a thickness of 17.5 microns to 27.5 microns by dipping the steel substrate into the primer It was then cured at 200 F for 30 minutes.
  • the sample was then subjected to the corrosion test described above for five weeks.
  • the adhesion was good based on a tape test (ASTM D3359).
  • the average creep distance was 1.5 millimeters and there was no blistering.
  • Minor edge corrosion was caused by nonuniform coverage of the primer on the edges not due to the plasma deposition layer. This problem could be eliminated by a different primer application method (e.g. vacuum deposition polymerization or electrocoating).
  • Substrate Zinc-phosphated Chromio Acid Rinsed Steel (available from ACT Corp. product designation GMC-92C; C168 C20 DlW)
  • O 2 plasma pretreatment oonditions DC power was 12 watts and 600-800 volts: energy input per mass was 0.25 gigaJoules per kilogram; oxygen gas flow rate was 2 standard cubic centimeter per minute (sccm); system pressure was 30 milliTorr; and power duration was 2 minutes.
  • primer coating The substrate was removed from the vacuum chamber and the primer was applied.
  • the primer which was applied was our most preferred primer containing methoxysilane functional group. This resin is described in Kanegafuchi Patent No. U.S. 4,801,658.
  • the primer was applied to a thickness of 17.5 microns to 27.5 microns by dipping the steel substrate into the primer It was then cured at 200 F. for 30 minutes
  • the sample was then subjected to the corrosion test described above for five weeks.
  • the adhesion was good based on a tape test (ASTM D3359).
  • the average creep distance was 0.9 millimeters and there was no blistering.
  • Very minor edge corrosion was observed and is thought to be caused by nonuniform coverage of the primer on the edges not due to the plasma deposition layer. This problem could be eliminated by a different primer application method (e.g. vacuum deposition polymerization or electrocoating).
  • Substrate Zinc-phosphated Chromic Acid Rinsed Galvinized Steel (available from ACT Corporation as product desiqnation GMC 90E Electro G1V70/70; C168 C20 DIW)
  • O 2 plasma pretreatment conditions DC power was 12 watts and 600-800 volts; energy input per mass was 0.25 gigaJoules per kilogram; oxygen gas flow rate was 2 standard cubic centimeter per minute (sccm); system pressure was 30 milliTorr; and power duration was 2 minutes.
  • primer coating The substrate was removed from the vacuum chamber and the primer was applied.
  • the primer which was applied was our most preferred primer containing methoxysilane functional group. This resin is described in Kanegafuchi Patent No. U.S. 4,801,658.
  • the primer was applied to a thickness of 17.5 microns to 27.5 microns by dipping the steel substrate into the primer. It was then cured at 200 F. for 30 minutes.
  • the sample was then subjected to the corrosion test described above for five weeks.
  • the adhesion was good based on a tape test (ASTM D3359).
  • the average creep distance was 1.2 millimeters and there was no blistering.
  • Very minor edge corrosion was observed and is thought to be caused by nonuniform coverage of the primer on the edges not due to the plasma deposition layer. This problem could be eliminated by a different primer application method (e.g. vacuum deposition polymerization or electrocoating).
  • Substrate Galvinized Steel available from ACT Corporation as product designation GMC 90E Elec Zinc G70/70; Clean
  • O 2 plasma pretreatment conditions DC power was 12 watts and 600-800 volts; energy input per mass was 0.25 gigaJoules per kilogram; oxygen gas flow rate was 2 standard cubic centimeter per minute (sccm); system pressure was 30 milliTorr; and power duration was 2 minutes.
  • a coating of organic film primer was carried out with parylene®C compound (available from Nova Tran Corp. a subsidiary of Union Carbide Corp.) using the vacuum deposition polymerization method described in Professor Yasuda's publication entitled Polymerization of Para-Xylylene Derivatives (Parylene Polymerization).
  • the primer was applied to a thickness of 10.0 microns at room temperature.
  • the sample was then subjected to the corrosion test described above for five weeks.
  • the adhesion was good based on a tape test (ASTM D3359).
  • the average creep distance was 1.4 millimeters and there was no blistering.
  • the edge corrosion protection was very good.
  • Substrate Bare Steel (available from ACT Corp. product designation GMC 92A; clean cold rolled steel).
  • This example is included to show that post treatment of the plasma film layer is a viable option and can result in improved corrosion resistance.
  • O 2 plasma pretreatment conditions DC power was 12 watts and 600-800 volts; energy input per mass was 0.25 gigaJoules per kilogram; oxygen gas flow rate was 2 standard cubic centimeter per minute (sccm); system pressure was 50 milliTorr; and power duration was 2 minutes.
  • Deposition of plasma methane polymer using methane gas DC power was 5 watts and 500-600 volts; energy input per mass was 0.21 gigaJoules per kilogram; methane gas flow rate was 2 standard cubic centimeter per minute (sccm); system pressure was 50 milliTorr; and power duration was 2 minutes.
  • the methane plasma layer was post treated with carbon dioxide plasma gas.
  • the conditions were as follows DC power was 5 watts and 500-600 volts; energy input per mass was 0.076 gigaJoules per kilogram; carbon dioxide gas flow rate was 2 standard cubic centimeter per minute (sccm); system pressure was 50 milliTorr; and power duration was 2 minutes.
  • the post treated substrate was then subjected to electrodeposition of cathodic epoxy amine resin.
  • the cathodic electrodepositable coating was prepared by using 4 parts (volume) of PPG's E5625®resin, 1 part (volume) of PPG's E5605®pigment paste, and 4 parts (volume) of deionized water.
  • the cathodic electrodeposition was carried out under conditions well known to one skilled in the art. The electrodeposition took place at 200 volts for a time period of two minutes. The electrodeposited film was then baked at 350 F. for 30 minutes. The film thickness was about 25 microns.

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US07/480,356 1990-02-14 1990-02-14 Method of coating steel substrate using low temperature plasma processes and priming Expired - Lifetime US4980196A (en)

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Application Number Priority Date Filing Date Title
US07/480,356 US4980196A (en) 1990-02-14 1990-02-14 Method of coating steel substrate using low temperature plasma processes and priming
PCT/US1990/006405 WO1991012092A1 (en) 1990-02-14 1990-11-09 Method of coating steel substrate using low temperature plasma processes and priming
DE69030107T DE69030107T2 (de) 1990-02-14 1990-11-09 Verfahren zum beschichten von stahl unter verwendung von niedertemperatur-plasmaprozessen und grundierung
ES90916927T ES2098275T3 (es) 1990-02-14 1990-11-09 Procedimiento de revestimiento de un sustrato de acero utilizando tecnologia de plasma a baja temperatura y una imprimacion.
EP90916927A EP0515373B1 (en) 1990-02-14 1990-11-09 Method of coating steel substrate using low temperature plasma processes and priming
JP2515713A JP2843670B2 (ja) 1990-02-14 1990-11-09 低温プラズマ処理およびプライマー処理を用いる鋼基体のコーティング方法
BR909007994A BR9007994A (pt) 1990-02-14 1990-11-09 Processo para revestir um substrato de aco usando processos de plasma a baixa temperatura e uma camada de base
AU67216/90A AU652544B2 (en) 1990-02-14 1990-11-09 Method of coating steel substrate using low temperature plasma processes and priming
KR1019920701946A KR0143884B1 (ko) 1990-02-14 1990-11-09 저온 플라즈마 공정에 의한 강철 기재의 피복 및 하도 방법
CA002035991A CA2035991C (en) 1990-02-14 1991-02-08 Method of coating steel substrate using low temperature plasma processes and priming
NZ237089A NZ237089A (en) 1990-02-14 1991-02-12 Corrosion-protection of steel by treating it with a gas plasma, depositing a film of an organosilane on it, and applying a primer coating which reacts with the organosilane
MX024521A MX173224B (es) 1990-02-14 1991-02-13 Metodo para revestir un substrato de acero para protegerlo de la corrosion, mediante plasma a baja emperatura e imprimacion

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US5236564A (en) * 1989-05-09 1993-08-17 Basf Lacke + Farben Aktiengesellschaft Process for the coating of electrically conducting substrates
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US5182000A (en) * 1991-11-12 1993-01-26 E. I. Du Pont De Nemours And Company Method of coating metal using low temperature plasma and electrodeposition
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US5312529A (en) * 1991-11-12 1994-05-17 E. I. Du Pont De Nemours And Company Method of coating metal using low temperature plasma and electrodeposition
DE19523208A1 (de) * 1995-06-27 1997-01-02 Behr Gmbh & Co Wärmeübertrager, insbesondere Verdampfer für eine Kraftfahrzeug-Klimaanlage
US5874127A (en) * 1995-08-16 1999-02-23 Ciba Vision Corporation Method and apparatus for gaseous treatment
US6137231A (en) * 1996-09-10 2000-10-24 The Regents Of The University Of California Constricted glow discharge plasma source
US20050061024A1 (en) * 1997-12-04 2005-03-24 Korea Institute Of Science And Technology And Lg Electronics Inc. Plasma polymerization enhancement of surface of metal for use in refrigerating and air conditioning
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DE69030107T2 (de) 1997-08-28
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MX173224B (es) 1994-02-09
CA2035991A1 (en) 1991-08-15
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WO1991012092A1 (en) 1991-08-22
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BR9007994A (pt) 1992-11-17
DE69030107D1 (de) 1997-04-10
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